The type and magnitude of stress in electroless Ni–Cu–P deposits on Al were manipulated by controlling the concentration of saccharin in the plating solution. Tensile, zero, and compressive stress of the electroless Ni–Cu–P deposits was obtained with 0, 8, and 10 g/l saccharin for studying the effect of stress on the diffusion and crystallization behavior of the deposit. The effect of stress on the diffusion behavior of Cu, Ni, and Al elements during annealing was investigated. Interdiffusion between Al and Ni in an amorphous Ni–Cu–P/crystal Al diffusion couple is abated by the effects of amorphous structure, atomic affinity, and backstress. Therefore, the effect of stress on diffusion is manifested by Cu elemental diffusion. The tensile stress promotes the formation of Ni3P and the diffusion of Cu into the substrate.